CN105985521A - Polybenzimidazole imide and preparation method thereof - Google Patents
Polybenzimidazole imide and preparation method thereof Download PDFInfo
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- CN105985521A CN105985521A CN201510056614.6A CN201510056614A CN105985521A CN 105985521 A CN105985521 A CN 105985521A CN 201510056614 A CN201510056614 A CN 201510056614A CN 105985521 A CN105985521 A CN 105985521A
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- WGQYSDCOPXQXGA-UHFFFAOYSA-N O=C(c1c(C2=O)c(Cl)ccc1)N2c(cc1)ccc1Oc(cc1)ccc1N(C(c1cccc(Cl)c11)=O)C1=O Chemical compound O=C(c1c(C2=O)c(Cl)ccc1)N2c(cc1)ccc1Oc(cc1)ccc1N(C(c1cccc(Cl)c11)=O)C1=O WGQYSDCOPXQXGA-UHFFFAOYSA-N 0.000 description 1
- MSQGYVACVAASTG-UHFFFAOYSA-N c1nc(cc(cc2)-c(cc3)cc4c3nc[nH]4)c2[nH]1 Chemical compound c1nc(cc(cc2)-c(cc3)cc4c3nc[nH]4)c2[nH]1 MSQGYVACVAASTG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a polybenzimidazole imide. The polybenzimidazole imide has a structural formula as described in the specification. In the structural formula, m is an integer larger than or equal to 1; n is an integer larger than or equal to 0; an Ar1 group is connected with two imidazole rings to form a benzimidazole group; Ar2 is residues of diamine compounds; Ar3 is residues of diphenol compounds; the benzimidazole group exists in a 3- position and/or a 4- position of an imidoylben ring; and an oxygen atom exists in a 3- position and/or 4- position of the imidoylben ring. According to the invention, by adopting benzimidazole, a bisphenol monomer and a bis-substituted imide monomer as raw materials, the polybenzimidazole imide is prepared through an aromatic nucleophilic substitution reaction. The polybenzimidazole imide has the characteristics of good heat resistance, good dissolvability, good processability, good mechanical properties, etc., and has good application prospects in the fields of high-temperature-resistant engineering plastics, proton exchange membranes, fibers, adhesives, coatings, advanced composite materials, etc.
Description
Technical field
The invention belongs to polyimides preparation method technical field, be specifically related to a kind of polybenzimidazoles acid imide and
Its preparation method.
Background technology
Polyimides is the resin material of a class excellent combination property, has good heat stability, excellent machine
Tool performance, preferable dimensional stability, excellent chemical stability, high-breakdown-voltage, low-k, height
The advantage such as anti-flammability, low-expansion coefficient, is widely used in electronic apparatus, Aero-Space, automobile, chemical industry machine
The high-tech areas such as tool.
Polybenzimidazoles is the high performance engineering plastics of a class excellent combination property, especially its thermostability and machinery
Performance highlights, and is widely used in the fields such as Aero-Space, electronic apparatus, fuel battery proton exchange film, and existing oneself becomes
Important materials for national economy, sophisticated technology and new high-tech industry.
At present, numerous research institutions have carried out relevant benzimidazole unit and combine with polyimides and obtain polyphenyl also
The research of imidazoles acid imide material achieved with correlational study achievement, such as Nippon Mektron KK
CN1446840A, Beijing University of Chemical Technology martial virtue treasure CN102345177A, Donghua University's Zhang Qinghua
CN102604091A, Donghua University Yu Xin sea CN102942310A and CN103102796A, Jilin University
In knowing, the patent documentations such as intelligent CN103422253A report some polyimides materials containing benzimidazole unit
Material.But, these materials all use the dianhydride containing glyoxaline structure or the diamidogen containing glyoxaline structure and conventional two
Prepared by amine or dianhydride polyreaction, this preparation method complex steps, operation complexity, significantly limit material
Research and application.
Summary of the invention
The invention provides a kind of polybenzimidazoles acid imide, it has good heat resistance and mechanical performance,
Be suitable for be molded, extrude, mold, melt spinning and solvent spinning are processed, at resistant to elevated temperatures engineering plastics, proton
The association areas such as exchange membrane, fiber, adhesive, coating and advanced composite material have a good application prospect.
Present invention also offers one and prepare the imido method of this polybenzimidazoles, the method uses C-N even
Connection nucleophilic substitution, crosses nucleophilic displacement of fluorine by the N-H push-to on also imidazole ring and gathers with disubstituted dant monomer
Close and form polybenzimidazoles acid imide.
The structural formula of the polybenzimidazoles imide resin that the present invention provides is as follows:
Wherein, m is greater than or equal to the integer of 1, and n is greater than or equal to the integer of 0；Ar1Group connects
Two imidazole rings form benzimidazole group, Ar2It is the residue of diamine compounds, Ar3It is diphenols chemical combination
The residue of thing；Benzimidazole group is present in 3-position and/or the 4-position of acid imide phenyl ring；Oxygen atom is present in acyl
The 3-position of imines phenyl ring and/or 4-position.
As preferably, m, n value in structure above is the integer between 10 to 1000.
Described Ar1Can be one or more in following groups:
Described Ar2Can be one or more in following groups:
Described Ar3Can be one or more in following groups:
That is, the present invention introduces benzimidazole unit, the polybenzimidazoles obtained in the stiff backbone of polyimides
Imide resin has good heat resistance and mechanical performance.When solvent is N-Methyl pyrrolidone, polyphenyl
And imidazoles acid imide is time in this solvent, concentration is 0.5g/dL, by determination of ubbelohde viscometer its at 30 DEG C
Logarithmic viscosity number is 0.16dL/g～1.20dL/g, preferably 0.3dL/g～0.8dL/g, more preferably 0.35
DL/g～0.55dL/g.Measuring its glass transition temperature by differential scanning calorimetry is 180 DEG C～350 DEG C；
It is preferably 200 DEG C～340 DEG C；More preferably 250 DEG C～330 DEG C.By thermal gravimetric analyzer measure its 5%
Heat decomposition temperature is 400 DEG C～550 DEG C；It is preferably 420 DEG C～520 DEG C；More preferably 450 DEG C～500 DEG C.
Tensile stress is 70MPa～120MPa, preferably 80～110MPa；Stretch modulus be 2000MPa～
3000Mpa, preferably 2200MPa～2800MPa；Elongation at break is 5.0%～20%, is preferably
10%～20%.
Therefore, this polybenzimidazoles imide resin has good using value, such as, can be applicable to high temperature ring
The correlation technique necks such as border engineering plastics, PEM, fiber, adhesive, coating and advanced composite material
Territory.
The imido method of above-mentioned polybenzimidazoles of preparing that the present invention provides is: by benzimidazole monomer, bis-phenol
Monomer and the mixing of disubstituted dant monomer, benzimidazole ring and disubstituted dant monomer generation aromatic nucleophilic
Substitution reaction, simultaneously biphenol monomer and disubstituted dant monomer generation aromatic nucleophilic substitution reaction, shape after condensation
Become polybenzimidazoles acid imide.
That is, this preparation method is specific as follows:
Benzimidazole monomer, biphenol monomer, disubstituted dant monomer, base catalysis is added in reaction vessel
Agent, organic solvent, water entrainer, fully mixing carry out aromatic nucleophilic substitution reaction, and its reaction scheme is as follows,
After reaction cool down, reactant liquor is poured in precipitant, refilter, collect precipitation after fully wash, be dried, system
Obtain polybenzimidazoles imide resin；
Wherein, X is nitro, or halogen atom fluorine, chlorine, and X is in 3-position or the 4-of acid imide phenyl ring
Position；M is greater than or equal to the integer of 1, and n is greater than or equal to the integer of 0.
Described base catalyst be selected from but be not limited to carbonate (such as potassium carbonate, sodium carbonate, lithium carbonate etc.),
Bicarbonate (such as sodium bicarbonate, potassium bicarbonate etc.), organic base (as triethylamine, tri-n-butylamine, pyridine,
Pyrimidine, isoquinolin etc.), the alkali metal salt of alcohol is (such as Feldalat NM, sodium tert-butoxide, potassium tert-butoxide, tert-butyl alcohol lithium
Deng), the compound such as metal hydride (such as sodium hydride, lithium hydride, hydrofining etc.).
As preferably, described base catalyst consumption be benzimidazole and the 100% of bis-phenol integral molar quantity～
150%.
Described organic solvent includes but not limited to N, N '-dimethylformamide, N, N '-dimethyl acetylamide, N-
N-methyl-2-2-pyrrolidone N, dimethyl sulfoxide, sulfolane, diphenyl sulphone (DPS) etc..
Described water entrainer does not limits, and can be toluene, chlorobenzene, dimethylbenzene, dichloro-benzenes etc..
As preferably, described nucleophilic substitution is to carry out in inert gas shielding atmosphere.
As preferably, in course of reaction, reaction system is warming up to 160 DEG C～250 DEG C.
As preferably, the response time of described aromatic nucleophilic substitution reaction is 6 hours～24 hours, more excellent
Elect 8 hours～12 hours as.
As preferably, the molecular weight of the prepared polybenzimidazoles imide resin of end-capping reagent regulation and control can be used, i.e.
When adding end-capping reagent after nucleophilic substitution, continuation reaction certain time blocks.Described end-capping reagent is permissible
For having the compound of following structure:
Wherein X is nitro or the halogen atom such as fluorine, chlorine, can be in 3-position or 4-position.End-capping reagent can be N-
Phenyl-3-fluoro phthalimide, N-phenyl-4-fluoro phthalimide, N-phenyl-3-chloro are adjacent
Phthalimide, N-phenyl-4-chlorophthalimide, N-phenyl-3-nitroaromatic phthalyl are sub-
Amine, N-phenyl-4-nitroaromatic phthalimide etc..The time preferably 1 of reaction is continued after adding end-capping reagent
Hour～2 hours.
Compared with existing preparation method, it is sub-that the present invention uses nucleophilic substitution condensation to prepare polybenzimidazoles acyl
Amine, the method is simple, and cost is relatively low.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, it is necessary to be pointed out that the present embodiment
It is served only for the present invention is further detailed, it is impossible to be interpreted as limiting the scope of the invention.This neck
Person skilled in the art in territory can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1:
In the present embodiment, polybenzimidazoles acid imide has a following structural formula:
The imido reaction scheme of above-mentioned polybenzimidazoles is as follows:
The imido preparation method of above-mentioned polybenzimidazoles is as follows:
4.96g (0.01mol) 4,4 '-bis-fluoro dant monomers are added in the 250mL there-necked flask of dried and clean,
1.64g (0.007mol) benzimidazole, 0.685g (0.003mol) bisphenol-A, 1.16g (0.011mol) carbonic acid
Sodium, 40mL dimethylbenzene, 40mL METHYLPYRROLIDONE, under nitrogen protection, 200 DEG C of backflow band water
React 12 hours；It is then cooled to room temperature, reactant liquor is poured slowly in 500mL ethanol, filters,
Gained filter cake ethanol boils to be washed 2 times, be placed in 120 DEG C of baking ovens and be dried 8 hours, obtain faint yellow poly-
Benzimidazole acid imide powder 6.62g, productivity is 91%.
This polybenzimidazoles acid imide is carried out performance test, and result is as follows:
(1) logarithmic viscosity number measured in the METHYLPYRROLIDONE that 30 DEG C of concentration are 0.5g/dL
For 0.38dL/g；
(2) glass transition temperature measured by differential scanning calorimetry is 322 DEG C；
(3) 5% heat decomposition temperature measured by thermal gravimetric analyzer is 432 DEG C.
Imido for this polybenzimidazoles METHYLPYRROLIDONE solution (solid content 10%) is uniformly coated
On clean glass plate, glass plate is positioned in drying baker, heats up according to follow procedure: 80 DEG C,
8 hours；100 DEG C, 1 hour；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；
300 DEG C, 1 hour.After temperature is down to room temperature, takes out glass plate, is placed on demoulding in water, then by thin
Film is placed in 100 DEG C of drying baker and is dried except water, obtains polybenzimidazole imide membrane, and its thickness is 20um.
The hot property of its film, mechanical performance see attached list 1.
Embodiment 2:
In the present embodiment, polybenzimidazoles acid imide has a following structural formula:
The imido reaction scheme of above-mentioned polybenzimidazoles is as follows:
The imido preparation method of above-mentioned polybenzimidazoles is as follows:
4.96g (0.01mol) 4,4 '-bis-fluoro dant monomers are added in the 250mL there-necked flask of dried and clean,
1.17g (0.005mol) benzimidazole, 1.14g (0.005mol) bisphenol-A, 1.16g (0.011mol) carbonic acid
Sodium, 40mL dimethylbenzene, 40mL METHYLPYRROLIDONE, under nitrogen protection, 200 DEG C of backflow band water
React 12 hours；It is then cooled to room temperature, reactant liquor is poured slowly in 500mL ethanol, filters,
Gained filter cake ethanol boils to be washed 2 times, be placed in 120 DEG C of baking ovens and be dried 8 hours, obtain faint yellow poly-
Benzimidazole acid imide powder 6.76g, productivity is 93%.
This polybenzimidazoles acid imide is carried out performance test, and result is as follows:
(1) logarithmic viscosity number measured in the METHYLPYRROLIDONE that 30 DEG C of concentration are 0.5g/dL
For 0.36dL/g；
(2) glass transition temperature measured by differential scanning calorimetry is 317 DEG C；
(3) 5% heat decomposition temperature measured by thermal gravimetric analyzer is 421 DEG C.
Imido for this polybenzimidazoles METHYLPYRROLIDONE solution (solid content 10%) is coated uniformly on clean
On clean glass plate, glass plate is positioned in drying baker, heats up according to follow procedure: 80 DEG C, 8
Hour；100 DEG C, 1 hour；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；
300 DEG C, 1 hour.After temperature is down to room temperature, takes out glass plate, is placed on demoulding in water, then by thin
Film is placed in 100 DEG C of drying baker and is dried except water, obtains polybenzimidazole imide membrane, and its thickness is 20um.
The hot property of its film, mechanical performance see attached list 1.
Embodiment 3:
In the present embodiment, polybenzimidazoles acid imide has a following structural formula:
The imido reaction scheme of above-mentioned polybenzimidazoles is as follows:
The imido preparation method of above-mentioned polybenzimidazoles is as follows:
4.96g (0.01mol) 4,4 '-bis-fluoro dant monomers are added in the 250mL there-necked flask of dried and clean,
0.70g (0.003mol) benzimidazole, 1.60g (0.007mol) bisphenol-A, 1.16g (0.011mol) sodium carbonate,
40mL dimethylbenzene, 40mL METHYLPYRROLIDONE, under nitrogen protection, 200 DEG C of backflow band water reactions
12 hours；It is then cooled to room temperature, being poured slowly into by reactant liquor in 500mL ethanol, filter, gained is filtered
Cake ethanol boils to be washed 2 times, be placed in 120 DEG C of baking ovens be dried 8 hours, obtain faint yellow polyphenyl miaow
Azoles acid imide powder 6.88g, productivity is 95%.
This polybenzimidazoles acid imide is carried out performance test, and result is as follows:
(1) logarithmic viscosity number measured in the METHYLPYRROLIDONE that 30 DEG C of concentration are 0.5g/dL
For 0.40dL/g；
(2) glass transition temperature measured by differential scanning calorimetry is 253 DEG C；
(3) 5% heat decomposition temperature measured by thermal gravimetric analyzer is 416 DEG C.
Imido for this polybenzimidazoles METHYLPYRROLIDONE solution (solid content 10%) is coated uniformly on clean
On clean glass plate, glass plate is positioned in drying baker, heats up according to follow procedure: 80 DEG C, 8
Hour；100 DEG C, 1 hour；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；
300 DEG C, 1 hour.After temperature is down to room temperature, takes out glass plate, is placed on demoulding in water, then by thin
Film is placed in 100 DEG C of drying baker and is dried except water, obtains polybenzimidazole imide membrane, and its thickness is 20um.
The hot property of its film, mechanical performance see attached list 1.
Embodiment 4:
In the present embodiment, polybenzimidazoles acid imide has a following structural formula:
The imido reaction scheme of above-mentioned polybenzimidazoles is as follows:
The imido preparation method of above-mentioned polybenzimidazoles is as follows:
4.96g (0.01mol) 4,4 '-bis-fluoro dant monomers are added in the 250mL there-necked flask of dried and clean,
1.41g (0.006mol) benzimidazole, 1.27g (0.004mol) phenolphthalein, 1.41g (0.011mol) potassium carbonate,
40mL dimethylbenzene, 40mL sulfolane, under nitrogen protection, 180 DEG C of backflow band water react 12 hours；
It is then cooled to room temperature, reactant liquor is poured slowly in 500mL ethanol, filters, gained filter cake ethanol
Boil and wash 2 times, be placed in 120 DEG C of baking ovens be dried 8 hours, obtain faint yellow polybenzimidazoles acid imide
Powder 6.87g, productivity is 90%.
This polybenzimidazoles acid imide is carried out performance test, and result is as follows:
(1) logarithmic viscosity number measured in the METHYLPYRROLIDONE that 30 DEG C of concentration are 0.5g/dL
For 0.41dL/g；
(2) glass transition temperature measured by differential scanning calorimetry is 332 DEG C；
(3) 5% heat decomposition temperature measured by thermal gravimetric analyzer is 420 DEG C.
Imido for this polybenzimidazoles METHYLPYRROLIDONE solution (solid content 10%) is coated uniformly on clean
On clean glass plate, glass plate is positioned in drying baker, heats up according to follow procedure: 80 DEG C, 8
Hour；100 DEG C, 1 hour；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；
300 DEG C, 1 hour.After temperature is down to room temperature, takes out glass plate, is placed on demoulding in water, then by thin
Film is placed in 100 DEG C of drying baker and is dried except water, obtains polybenzimidazole imide membrane, and its thickness is 20um.
The hot property of its film, mechanical performance see attached list 1.
Embodiment 5:
In the present embodiment, polybenzimidazoles acid imide has a following structural formula:
The imido reaction scheme of above-mentioned polybenzimidazoles is as follows:
The imido preparation method of above-mentioned polybenzimidazoles is as follows:
4.96g (0.01mol) 4,4 '-bis-fluoro dant monomers are added in the 250mL there-necked flask of dried and clean,
1.17g (0.005mol) benzimidazole, 1.59g (0.005mol) phenolphthalein, 1.41g (0.011mol) potassium carbonate,
40mL dimethylbenzene, 40mL sulfolane, under nitrogen protection, 180 DEG C of backflow band water react 12 hours；
It is then cooled to room temperature, reactant liquor is poured slowly in 500mL ethanol, filters, gained filter cake ethanol
Boil and wash 2 times, be placed in 120 DEG C of baking ovens be dried 8 hours, obtain faint yellow polybenzimidazoles acid imide
Powder 6.02g, productivity is 91%.
This polybenzimidazoles acid imide is carried out performance test, and result is as follows:
(1) logarithmic viscosity number measured in the METHYLPYRROLIDONE that 30 DEG C of concentration are 0.5g/dL
For 0.39dL/g；
(2) glass transition temperature measured by differential scanning calorimetry is 319 DEG C；
(3) 5% heat decomposition temperature measured by thermal gravimetric analyzer is 440 DEG C.
Imido for this polybenzimidazoles METHYLPYRROLIDONE solution (solid content 10%) is uniformly coated
On clean glass plate, glass plate is positioned in drying baker, heats up according to follow procedure: 80 DEG C,
8 hours；100 DEG C, 1 hour；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；
300 DEG C, 1 hour.After temperature is down to room temperature, takes out glass plate, is placed on demoulding in water, then by thin
Film is placed in 100 DEG C of drying baker and is dried except water, obtains polybenzimidazole imide membrane, and its thickness is 20um.
The hot property of its film, mechanical performance see attached list 1.
Embodiment 6:
In the present embodiment, polybenzimidazoles acid imide has a following structural formula:
The imido reaction scheme of above-mentioned polybenzimidazoles is as follows:
The imido preparation method of above-mentioned polybenzimidazoles is as follows:
4.96g (0.01mol) 4,4 '-bis-fluoro dant monomers are added in the 250mL there-necked flask of dried and clean,
0.94g (0.004mol) benzimidazole, 1.91g (0.006mol) phenolphthalein, 1.41g (0.011mol) potassium carbonate,
40mL dimethylbenzene, 40mL sulfolane, under nitrogen protection, 180 DEG C of backflow band water react 12 hours；
It is then cooled to room temperature, reactant liquor is poured slowly in 500mL ethanol, filters, gained filter cake ethanol
Boil and wash 2 times, be placed in 120 DEG C of baking ovens be dried 8 hours, obtain faint yellow polybenzimidazoles acid imide
Powder 6.79g, productivity is 87%.
This polybenzimidazoles acid imide is carried out performance test, and result is as follows:
(1) logarithmic viscosity number measured in the METHYLPYRROLIDONE that 30 DEG C of concentration are 0.5g/dL
For 0.35dL/g；
(2) glass transition temperature measured by differential scanning calorimetry is 316 DEG C；
(3) 5% heat decomposition temperature measured by thermal gravimetric analyzer is 415 DEG C.
Imido for this polybenzimidazoles METHYLPYRROLIDONE solution (solid content 10%) is coated uniformly on clean
On clean glass plate, glass plate is positioned in drying baker, heats up according to follow procedure: 80 DEG C, 8
Hour；100 DEG C, 1 hour；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；
300 DEG C, 1 hour.After temperature is down to room temperature, takes out glass plate, is placed on demoulding in water, then by thin
Film is placed in 100 DEG C of drying baker and is dried except water, obtains polybenzimidazole imide membrane, and its thickness is 20um.
The hot property of its film, mechanical performance see attached list 1.
Embodiment 7:
In the present embodiment, polybenzimidazoles acid imide has a following structural formula:
The imido reaction scheme of above-mentioned polybenzimidazoles is as follows:
The imido preparation method of above-mentioned polybenzimidazoles is as follows:
5.50g (0.01mol) 4,4 '-bis-nitroaromatic acid imide lists are added in the 250mL there-necked flask of dried and clean
Body, 2.34g (0.01mol) benzimidazole, 1.41g (0.011mol) potassium carbonate, 15mL toluene, 30mL N-
N-methyl-2-2-pyrrolidone N, under nitrogen protection, 200 DEG C of backflow band water react 12 hours；It is then cooled to
Room temperature, is poured slowly into reactant liquor in 500mL ethanol, filters, and gained filter cake ethanol boils to be washed 2 times, it
It is placed in 120 DEG C of baking ovens and is dried 8 hours, obtain faint yellow polybenzimidazoles acid imide powder 6.76g, produce
Rate is 93%.
This polybenzimidazoles acid imide is carried out performance test, and result is as follows:
(1) logarithmic viscosity number measured in the METHYLPYRROLIDONE that 30 DEG C of concentration are 0.5g/dL
For 0.50dL/g；
(2) glass transition temperature measured by differential scanning calorimetry is 336 DEG C；
(3) 5% heat decomposition temperature measured by thermal gravimetric analyzer is 483 DEG C.
Embodiment 8:
In the present embodiment, polybenzimidazoles acid imide has a following structural formula:
The imido reaction scheme of above-mentioned polybenzimidazoles is as follows:
The imido preparation method of above-mentioned polybenzimidazoles is as follows:
5.29g (0.01mol) 3,3 '-bis-chloro dant monomers are added in the 250mL there-necked flask of dried and clean,
2.34g (0.01mol) benzimidazole, 1.41g (0.011mol) potassium carbonate, 15mL toluene, 30mL N-first
Base-2-Pyrrolidone, under nitrogen protection, 200 DEG C of backflow band water react 12 hours；It is then cooled to room
Temperature, is poured slowly into reactant liquor in 500mL ethanol, filters, and gained filter cake ethanol boils washes 2 times, afterwards
It is placed in 120 DEG C of baking ovens and is dried 8 hours, obtain faint yellow polybenzimidazoles acid imide powder 5.62g, productivity
It is 77%.
This polybenzimidazoles acid imide is carried out performance test, and result is as follows:
(1) logarithmic viscosity number measured in the METHYLPYRROLIDONE that 30 DEG C of concentration are 0.5g/dL
For 0.16dL/g；
(2) glass transition temperature measured by differential scanning calorimetry is 340 DEG C；
(3) 5% heat decomposition temperature measured by thermal gravimetric analyzer is 465 DEG C.
Embodiment 9:
In the present embodiment, polybenzimidazoles acid imide has a following structural formula:
The imido reaction scheme of above-mentioned polybenzimidazoles is as follows:
The imido preparation method of above-mentioned polybenzimidazoles is as follows:
2.48g (0.005mol) 4,4 '-bis-fluoro acid imide lists are added in the 250mL there-necked flask of dried and clean
Body, 2.48g (0.005mol), 3,3 '-bis-fluoro dant monomers, 2.34g (0.01mol) benzimidazole, 1.41g
(0.011mol) potassium carbonate, 15mL toluene, 30mL METHYLPYRROLIDONE, under nitrogen protection,
200 DEG C of backflow band water react 12 hours；It is then cooled to room temperature, reactant liquor is poured slowly into 500mL
In ethanol, filter, gained filter cake ethanol boils to be washed 2 times, be placed in 120 DEG C of baking ovens be dried 8 hours,
Obtaining faint yellow polybenzimidazoles acid imide powder 8.37g, productivity is 89%.
This polybenzimidazoles acid imide is carried out performance test, and result is as follows:
(1) logarithmic viscosity number measured in the METHYLPYRROLIDONE that 30 DEG C of concentration are 0.5g/dL
For 0.27dL/g；
(2) glass transition temperature measured by differential scanning calorimetry is 325 DEG C；
(3) 5% heat decomposition temperature measured by thermal gravimetric analyzer is 523 DEG C.
Embodiment 10:
In the present embodiment, polybenzimidazoles acid imide has a following structural formula:
The imido reaction scheme of above-mentioned polybenzimidazoles is as follows:
The imido preparation method of above-mentioned polybenzimidazoles is as follows:
7.07g (0.01mol) 4,4 '-bis-fluoro dant monomers are added in the 250mL there-necked flask of dried and clean,
2.34g (0.01mol) benzimidazole, 1.41g (0.011mol) potassium carbonate, 15mL toluene, 30mL N-first
Base-2-Pyrrolidone, under nitrogen protection, 200 DEG C of backflow band water react 12 hours；It is then cooled to room
Temperature, is poured slowly into reactant liquor in 500mL ethanol, filters, and gained filter cake ethanol boils washes 2 times, afterwards
It is placed in 120 DEG C of baking ovens and is dried 8 hours, obtain faint yellow polybenzimidazoles acid imide powder 8.37g, productivity
It is 89%.
This polybenzimidazoles acid imide is carried out performance test, and result is as follows:
(1) logarithmic viscosity number measured in the METHYLPYRROLIDONE that 30 DEG C of concentration are 0.5g/dL
For 0.41dL/g；
(2) glass transition temperature measured by differential scanning calorimetry is 314 DEG C；
(3) 5% heat decomposition temperature measured by thermal gravimetric analyzer is 429 DEG C.
Table 1, embodiment 1-6 prepare polybenzimidazoles acid imide hot property and the sign of mechanical performance.
aAt 30 DEG C, the concentration of mensuration is that 0.5g/dL polybenzimidazoles acid imide is at METHYLPYRROLIDONE solution
In logarithmic viscosity number.bUnder nitrogen atmosphere, heating rate is 20 DEG C/min, the glass transition temperature of mensuration
Degree.
cUnder nitrogen atmosphere, temperature during thermal weight loss 5%.
Benzimidazole, biphenol monomer, the combination in any of disubstituted dant monomer in preparation method of the present invention
Realize the imido preparation of polybenzimidazoles.Do not repeat them here.
Technical scheme has been described in detail by embodiment described above, it should be understood that above institute
State the specific embodiment of the only present invention, be not limited to the present invention, all institutes in the spirit of the present invention
Any amendment of making, supplement or similar fashion replacement etc., should be included within the scope of the present invention.
Claims (10)
1. a polybenzimidazoles acid imide, is characterized in that: structural formula is:
Wherein, m is greater than or equal to the integer of 1, and n is greater than or equal to the integer of 0；Ar1Group connects
Two imidazole rings form benzimidazole group, Ar2It is the residue of diamine compounds, Ar3It is diphenols chemical combination
The residue of thing；Benzimidazole group is present in 3-position and/or the 4-position of acid imide phenyl ring；Oxygen atom is present in acyl
The 3-position of imines phenyl ring and/or 4-position.
Polybenzimidazoles acid imide the most according to claim 1, its feature: described Ar1It is following
One or more in group:
Polybenzimidazoles acid imide the most according to claim 1, its feature:
Described Ar2It is one or more in following groups:
Polybenzimidazoles acid imide the most according to claim 1, its feature:
Described Ar3It is one or more in following groups:
Polybenzimidazoles acid imide the most according to claim 1, is characterized in that: polybenzimidazoles acyl is sub-
When amine concentration in N-Methyl pyrrolidone is 0.5g/dL, measure its ratio by Ubbelohde viscometer at 30 DEG C
Dense log viscosities is 0.16dL/g～1.20dL/g；Preferably 0.3dL/g～0.8dL/g, more preferably 0.35
DL/g～0.55dL/g.
Polybenzimidazoles acid imide the most according to claim 1, is characterized in that: by differential scanning amount
It is 180 DEG C～350 DEG C that full-boiled process measures its glass transition temperature；It is preferably 200 DEG C～340 DEG C；More excellent
Elect 250 DEG C～330 DEG C as.
Polybenzimidazoles acid imide the most according to claim 1, is characterized in that: pass through thermogravimetic analysis (TGA)
It is 400 DEG C～550 DEG C that instrument measures its 5% heat decomposition temperature；It is preferably 200 DEG C～340 DEG C；More preferably
410 DEG C～450 DEG C.
Polybenzimidazoles acid imide the most according to claim 1, is characterized in that: tensile stress is 70
MPa～120MPa；Stretch modulus is 2000MPa～3000Mpa；Elongation at break is 5.0%～20%.
9. the imido preparation method of polybenzimidazoles as described in any claim in claim 1 to 8
It is characterized in that: in reaction vessel, add benzimidazole monomer, biphenol monomer, disubstituted dant monomer, alkali
Property catalyst, organic solvent, water entrainer, fully mix, carry out following aromatic nucleophilic substitution reaction, after reaction
Cooling, reactant liquor is poured in precipitant, refilter, collect precipitation after fully wash, be dried, prepare polyphenyl
And imidazoles imide resin,
Wherein, X is nitro, or halogen atom fluorine, chlorine, and X is in 3-position or the 4-of acid imide phenyl ring
Position.
The imido preparation method of polybenzimidazoles the most according to claim 9, it is characterised in that institute
Stating base catalyst is carbonate, bicarbonate, organic amine, the alkali metal salt of alcohol or metal hydride, consumption
For benzimidazole and the 100% of bis-phenol integral molar quantity～150%；
As preferably, described aromatic nucleophilic substitution reaction is to carry out in inert gas shielding atmosphere；In reaction
During, temperature of reaction system is between 150 DEG C～250 DEG C；
As preferably, described organic solvent is DMF, N,N-dimethylacetamide, ring
Fourth sulfone, methyl sulfoxide, N-Methyl pyrrolidone, diphenyl sulphone (DPS), water entrainer can be toluene, chlorobenzene, dimethylbenzene,
Dichloro-benzenes.
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| CN109503835A (en) * | 2018-09-20 | 2019-03-22 | 中国科学院宁波材料技术与工程研究所 | A kind of polyetherimide and preparation method thereof |
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